DUMBOdqSPC5sq: 2D SPC5 2Q-1Q correlation with DUMBO decoupling pulse program

Since non-phase cycling is applied to the SPC5 excitation pulse, four-phase cycling is applied to the detection pulse P1 for selecting the 0Q -> -1Q coherence order jump, and four-phase cycling is applied to the SPC5 reconversion pulse for filtering DQ coherences.

Code for Avance III spectrometers with topSpin2.1 operating system

;DUMBOdqSPC5sq
;2D DQ-SQ proton-proton shift correlation
;with SPC5 DQ excitation/reconversion
;with homonuclear DUMBO decoupling DQ evolution without prepulses during t1
;and windowed DUMBO acquisition
;S. P. Brown, A. Lesage, B. Elena and L. Emsley, J. Am. Chem. Soc. 126, 13230-13231 (2004).
;modified after Leskes, Madhu and Vega, Chem. Phys. Lett. to remove center artefact
;using STATES-TPPI
;This pulse program was written according to the corresponding DUMBO-sequence from
;the ENS-Lyon Pulse Program Library

;p9 2.4-4.5 usec, depending on probe deadtime, usually:
;for 200 and 300 MHz, CRAMPS probe required or use 4.5 usec,
;acqu or p9 must be as short as possible, avoiding dipolar coupling effects between DUMBO sequences,
;l11 or d9 must be as large as possible to improve S/N ratio, but keeping acqu positive and small,

;p1 : (90 + magic angle) degree 1H detection pulse
;p2 : presaturation 90 degree pulse
;p9 : acquisition window, 1.7-4.5 usec, depending on probe deadtime
;p10: dumbo-1   pulse for t2
;p20: dumber-22 pulse for t1

;d1 : recycle delay
;d5 : z filter delay, 0.1 μs or multiple of 1/cnst31, otherwise no signal
;d10: parameter for t1 value
;d20: delay between saturation pulses

;l0 : 0 as initial t1
;l1 : number SPC5 basic cycle elements, for protons 2-4 in real solids
;l3 : t1-increment multiplier, usually 2-4, to reduce required number of rows
;l11: number of oversampled data points to be averaged into one dwell point
;l20: # of pulses in saturation pulse train, 0 if undesired

;pl1 : 1H presaturation power
;pl7 : 1H power for SPC5, B1=5*cnst31 in Hz
;pl12: 1H power for pulses P1
;pl13: dumbo power
;sp1 : 1H power for windowed dumbo-1 (t2)
;sp2 : 1H power for dumber-22 (t1) (usually somewhat less power than sp1 since 
;      there is no window), set to pl13 as in setup experiments

;cnst3 : scaling factor for d3
;cnst31: spinning frequency (usually not more than 15 kHz possible)
;FnMode: undefined
;MC2   : STATES-TPPI
;NS    : =16*n
;zgoptns :-Dpresat or blank

;$COMMENT=homonuclear decoupling with w-DUMBO
;$CLASS=Solids
;$DIM=2D
;$TYPE=homonuclear decoupling
;$SUBTYPE=explicit acquisition
;$OWNER=hf

;cnst11 : to adjust t=0 for acquisition, if digmod = baseopt
"acqt0=1u*cnst11"


dwellmode auto

#include <Avancesolids.incl>
#include <Delayssolids.incl>

  "d3=cnst*p9"                 ;p9 sets the window to make sure it is in microseconds
  "d9=0.1u*(l11)"              ;set the sampling window, defined in Avancesolids.incl
  "blktr2 = 0.6u"              ;this opens the transmitter gate 0.6 usec before the
                               ;pulse, so the transmitter noise is not sampled
  "inf1=(l3*(2*d3+p20))*2"     ;t1 increment
  "sp1=pl13"

define delay dead
  "dead=1.2u"
define delay acqu              ;small window, defined by d3, 2.5-4.5 usec depending
  "acqu=2*p9-1.2u-d9-.1u"      ;on probe deadtime
                               ;acqu or p9 must be as short as possible, avoiding dipolar coupling effects
                               ;l11 or d9 must be as large as possible but keeping acqu positive
define delay cycle
  "cycle=4*p9+2*p10+.2u"
define loopcounter count
  "count=aq/cycle"             ;make sure td datapoints are sampled
define delay rest              ;make sure sampling proceeds throughout the sequence
  "rest=aq-(count*cycle)"

define loopcounter count1      ;for STATES-TPPI procedure
  "count1=td1/2"               ;and STATES cos/sin procedure

define pulse pul360
  "pul360=(1s/cnst31)/5"       ;360° pulse
define pulse pul90
  "pul90=(0.25s/cnst31)/5"     ; 90° pulse
define pulse pul270
  "pul270=(0.75s/cnst31)/5"    ;270° pulse

  "d31=1.0s/cnst31"

1 ze                           ;acquire into a cleared memory

2 d31

#ifdef presat                  ;set with -Dpresat
pres, d20                      ;delay between saturation pulses
  (p2 pl1 ph4):f1              ;saturation loop if required
  lo to pres times l20
#endif /* presat */

  d1                           ;recycle delay
  10u reset1:f1                ;synchronise pulse and detection RF
  1m rpp10                     ;reset phase list pointer
  1m rpp20                     ;reset phase list pointer
  1m rpp11
  1m rpp12
  1m rpp13
  1m rpp14
  10u pl7:f1
                               ;SPC5 DQ excitation:
3 pul90:f1  ph11 ipp13 ipp14   ;increment reconversion phase ph13 and ph14 pointers
  pul360:f1 ph12 ipp12         ;increment phase ph12 pointer
  pul270:f1 ph11 ipp11         ;increment phase ph11 pointer
  lo to 3 times l1

5 d3                           ;DQ evolution:
  d3
  (p20:sp2 ph20^):f1           ;dumber22
  d3
  d3
  (p20:sp2 ph20^):f1           ;dumber22
  lo to 5 times l0
                               ;phase correction, due to t1 evolution period,
                               ;is not applied to SPC5 DQ reconversion pulse. 
                               ;As a result, the 2D spectrum is shifted from F1=0.

6 pul90:f1  ph13 pl7:f1        ;SPC5 DQ reconversion:
  pul360:f1 ph14 ipp14         ;increment phase ph14 pointer
  pul270:f1 ph13 ipp13         ;increment phase ph13 pointer
  lo to 6 times l1

  d5 pl12:f1                   ;z filter delay
  STARTADC                     ;prepare adc for sampling, set reference frequency, 
                               ;defined in Avancesolids.incl
  RESETPHASE                   ;reset reference phase

  (p1 ph1):f1                  ;90° + magic angle detection pulse at pl12
  .1u DWL_CLK_ON
7 dead
  acqu
  d9 RG_ON
  .1u RG_OFF                   ;take l11  complex data points
  (p10:sp1  ph10^):f1          ;w-dumbo, use 24 usec at 600 MHz or higher
  dead
  acqu
  d9 RG_ON
  .1u RG_OFF
  (p10:sp1  ph10^):f1
  lo to 7 times count          ;make sure td points are sampled

  rest
  1u  DWL_CLK_OFF
  1m                           ;DQ filtering (four phase cycling):
  1m ip13*16384                ;increments all phases of ph13 by 90°
  1m ip14*16384                ;increments all phases of ph14 by 90°
  rcyc=2                       ;next scan
                               ;The rcyc statement is used for acquisition loops 
                               ;based on adc rather than go=label. Do not 
                               ;specify phase programs behind rcyc
  100m wr #0 if #0 zd          ;save data

  1m ip11*8192                 ;increments all phases of ph11 by 45°, 
                               ;90° phase for DQ coherence
  1m ip12*8192                 ;increments all phases of ph12 by 45°, 
                               ;90° phase for DQ coherence
  lo to 2 times 2              ;t1 quadrature detection

8 1m iu0                       ;increment counter l0 by 1
  lo to 8 times l3             ;for multiple t1 increment

  ;1m rp11                     ;reset all phases of ph11, ph12, ph13, and ph14 
  ;1m rp12                     ;to their original values, i.e. to the values they 
  ;1m rp13                     ;had before the first ip11, ip12, ip13, and ip14
  ;1m rp14                     ;in case of STATES remove semicolon at beginning of the 4 lines

  lo to 2 times count1         ;count1 = td1/2
  exit                         ;finished

ph1=  1 1 1 1 2 2 2 2 3 3 3 3 0 0 0 0
ph10= 0 2                      ;windowed dumbo phase during t2

ph11= (65536)     0 13107 26214 39322 52429 32768 45875 58982  6554 19661
ph12= (65536) 32768 45875 58982  6554 19661     0 13107 26214 39322 52429

ph13= (65536) 16384 29491 42598 55706  3277 49152 62259  9830 22937 36044
ph14= (65536) 49152 62259  9830 22937 36044 16384 29491 42598 55706  3277

                               ;an overall constant phase shift of π/2 is applied 
                               ;to the reconversion pulse phases ph13 and ph14 for time reversal

ph4= 0                         ;for presaturation pulse
ph20=0 2                       ;dumber22 phase during t1
ph30=0                         ;needed for acquisition, involved in RESETPHASE
ph31=0 2 0 2 1 3 1 3 2 0 2 0 3 1 3 1                   ;involved in STARTADC
                               ;ph31 = ph1 + 2*ph13 + 1

Example: L-Tyrosine.HCl

¹H DQ/SQ spectrum of L-Tyrosine.HCl in a 4-mm diameter 12-μLitre HRMAS rotor spinning at 14 kHz, three-channel probehead, and recorded with Bruker Avance III, 500 MHz WB US magnet.

References

Pinelopi Moutzouri, Manuel Cordova, Bruno Simões de Almeida, Daria Torodii, and Lyndon Emsley
Two-dimensional pure isotropic proton solid state NMR,
Angew. Chem. Int. Ed. 62, e202301963 (2023).
Open access

Renée Siegel, Luís Mafra, and João Rocha
Improving the ¹H indirect dimension resolution of 2D CRAMPS NMR spectra: A simulation and experimental investigation,
Solid State Nucl. Magn. Reson. 39, 81-87 (2011).
Abstract

Vadim Zorin and David Rice
Direct-drive waveform programming for solid-state NMR with the DD2 MR system,
PDF file

Andreas Brinkmann, Suresh Kumar Vasa, Hans Janssen, and Arno P. M. Kentgens
Proton micro-magic-angle-spinning NMR spectroscopy of nanoliter samples,
Chem. Phys. Lett. 485, 275-280 (2010).
Abstract

Luis Mafra, Renée Siegel, Christian Fernandez, Denis Schneider, Fabien Aussenac, and João Rocha
High-resolution ¹H homonuclear dipolar recoupling NMR spectra of biological solids at MAS rates up to 67 kHz,
J. Magn. Reson. 199, 111-114 (2009).
Abstract

RN-DQ/SQ-DUMBO excitation pulse sequence.

Luís Mafra, José R. B. Gomes, Julien Trébosc, João Rocha, and Jean-Paul Amoureux
¹H-¹H double-quantum CRAMPS NMR at very-fast MAS (ν_R = 35 kHz): A resolution enhancement method to probe ¹H-¹H proximities in solids,
J. Magn. Reson. 196, 88-91 (2009).
Abstract

BABA-DQ/SQ-SAM excitation pulse sequence.

Elodie Salager, Robin S. Stein, Chris J. Pickard, Bénédicte Elena, and Lyndon Emsley
Powder NMR crystallography of thymol,
Phys. Chem. Chem. Phys. 11, 2610-2621 (2009).
Abstract

Michal Leskes, P. K. Madhu, and Shimon Vega
Proton line narrowing in solid-state nuclear magnetic resonance: New insights from windowed phase-modulated Lee-Goldburg sequence,
J. Chem. Phys. 125, 124506/1-124506/18 (2006).
Abstract

Steven P. Brown, Anne Lesage, Bénédicte Elena, and Lyndon Emsley
Probing proton-proton proximities in the solid state: High-resolution two-dimensional ¹H-¹H double-quantum CRAMPS NMR spectroscopy,
J. Am. Chem. Soc. 126, 13230-13231 (2004).
Abstract

DQ-DUMBO excitation pulse sequence.

P. K. Madhu, Elena Vinogradov, and Shimon Vega
Multiple-pulse and magic-angle spinning aided double-quantum proton solid-state NMR spectroscopy,
Chem. Phys Lett. 394, 423-428 (2004).
Abstract

G. P. Drobny, J. R. Long, T. Karlsson, W. Shaw, J. Popham, N. Oyler, P. Bower, J. Stringer, D. Gregory, M. Mehta, and P. S. Stayton
Structural studies of biomaterials using double-quantum solid-state NMR spectroscopy,
Annu. Rev. Phys. Chem. 54, 531-571 (2003).
Abstract

T. Karlsson, A. Brinkmann, P. J. E. Verdegem, J. Lugtenburg, and M. H. Levitt
Multiple-quantum relaxation in the magic-angle-spinning NMR of ¹³C spin pairs,
Solid State Nucl. Magn. Reson. 14, 43-58 (1999).
Abstract

M. Hohwy, C. M. Rienstra, C. P. Jaroniec, and R. G. Griffin
Fivefold symmetric homonuclear dipolar recoupling in rotating solids: Application to double quantum spectroscopy,
J. Chem. Phys. 110, 7983-7992 (1999).
Abstract

M. Hohwy, H. J. Jakobsen, M. Edén, M. H. Levitt, and N. C. Nielsen
Broadband dipolar recoupling in the nuclear magnetic resonance of rotating solids: A compensated C7 pulse sequence,
J. Chem. Phys. 108, 2686-2694 (1998).
Abstract

W. A. Dollase, M. Feike, H. Förster, T. Schaller, I. Schnell, A. Sebald, and S. Steuernagel
A 2D ³¹P MAS NMR study of polycrystalline Cd₃(PO₄)₂,
J. Am. Chem. Soc. 119, 3807-3810 (1997).
Abstract

Y. K. Lee, N. D. Kurur, M. Helmle, O. G. Johannessen, N. C. Nielsen, and M. H. Levitt
Efficient dipolar recoupling in the NMR of rotating solids. A sevenfold symmetric radiofrequency pulse sequence,
Chem. Phys. Lett. 242, 304-309 (1995).
Abstract

A. Wokaun and R. R. Ernst
Selective detection of multiple quantum transitions in NMR by two-dimensional spectroscopy ,
Chem. Phys. Lett. 52, 407-412 (1977).
Abstract

Solid-state NMR bibliography for:

[Contact me] - Last updated February 24, 2020

General
PULPROG	DUMBOdqSPC5sq.ppm
TD	700
NS	16
DS	0
SWH [Hz]	20000.00
AQ [s]	0.0175500
RG	16
DW [µs]	25.000
DE [µs]	1.10
CNST3	1.0000000
CNST11	0.0000000
CNST31	14000.0000000
D1 [s]	5.00000000
d3 [s]	0.00000300
D5 [s]	0.00000100
d9 [s]	0.00000320
d31 [s]	0.00007143
inf1 [µs]	60.00
L0	0
L1	4
L3	1
L11	32
P9 [µs]	3.00
PL13 [dB]	3.00
ZGOPTNS
acqu [s]	0.00000150
count	291
count1	128
cycle [s]	0.00006020
de [µs]	0.00
dead [s]	0.00000120
rest [s]	0.00003180
Channel f1
CNST1	1.0000000
NUC1	1H
P1 [µs]	4.00
P10 [µs]	24.00
P20 [µs]	24.00
PL1 [dB]	9.80
PL1W [W]	33.58852005
PL7 [dB]	5.00
PL7W [W]	101.43571472
PL12 [dB]	9.80
PL12W [W]	33.58852005
pul270 [µs]	10.71
pul360 [µs]	14.29
pul90 [µs]	3.57
SFO1 [MHz]	500.1678149
SP1 [dB]	3.00
SP2 [dB]	3.00
SP2W [W]	160.76477051
SPNAM1	dumbo_1+0
SPNAM2	dumbo_1+0
SPOAL1	0.500
SPOAL2	0.500
SPOFFS1 [Hz]	0.00
SPOFFS2 [Hz]	0.00

	F2	F1
Experiment
PULPROG	DUMBOdqSPC5sq.ppm
AQ_mod	DQD
FnMODE		undefined
TD	700	256
NS	16
DS	0
TD0	1
Width
SW [ppm]	39.9866	33.3221
SWH [Hz]	20000.00	16666.666
IN_F [µs]		60.00
AQ [s]	0.0175500	0.0076800
Nucleus1
NUC1	1H	1H
O1 [Hz]	-2185.05	-2185.05
O1P [ppm]	-4.369	-4.369
SFO1 [MHz]	500.1678149	500.1678149
BF1 [MHz]	500.1700000	500.1700000

*** Outline ***

Code for Avance III spectrometers with topSpin2.1 operating system

Example: L-Tyrosine.HCl

References

Solid-state NMR bibliography for:

* Outline *